CN112745211B - Preparation method of isononanoic acid - Google Patents
Preparation method of isononanoic acid Download PDFInfo
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- CN112745211B CN112745211B CN202110084627.XA CN202110084627A CN112745211B CN 112745211 B CN112745211 B CN 112745211B CN 202110084627 A CN202110084627 A CN 202110084627A CN 112745211 B CN112745211 B CN 112745211B
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- XZOYHFBNQHPJRQ-UHFFFAOYSA-N 7-methyloctanoic acid Chemical compound CC(C)CCCCCC(O)=O XZOYHFBNQHPJRQ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002153 silicon-carbon composite material Substances 0.000 claims abstract description 41
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 21
- 238000003763 carbonization Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 229930006000 Sucrose Natural products 0.000 claims description 13
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 13
- 150000001299 aldehydes Chemical class 0.000 claims description 12
- 239000011541 reaction mixture Substances 0.000 claims description 12
- 239000005720 sucrose Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- JRPPVSMCCSLJPL-UHFFFAOYSA-N 7-methyloctanal Chemical compound CC(C)CCCCCC=O JRPPVSMCCSLJPL-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000012071 phase Substances 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 238000003980 solgel method Methods 0.000 claims description 4
- 238000006277 sulfonation reaction Methods 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000011161 development Methods 0.000 abstract description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 238000002390 rotary evaporation Methods 0.000 description 8
- 229960004793 sucrose Drugs 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- -1 aliphatic aldehydes Chemical class 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000005609 naphthenate group Chemical group 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 239000001116 FEMA 4028 Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- GOKIPOOTKLLKDI-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O.CC(O)=O GOKIPOOTKLLKDI-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 229960004853 betadex Drugs 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 150000002192 fatty aldehydes Chemical class 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of isononanoic acid, which is characterized in that isononanoic aldehyde is oxidized into isononanoic acid by taking sulfonated mesoporous silicon-carbon composite material as a catalyst and hydrogen peroxide as an oxidant. Compared with the prior art, the method has the characteristics of mild reaction conditions, few byproducts, high product purity, high yield, good economic benefit and the like, causes little pollution to the environment, and accords with the green development concept.
Description
Technical Field
The invention relates to the technical field of heterogeneous catalytic reaction, and particularly relates to a preparation method of isononanoic acid.
Background
The isononanoic acid has wide application, can be used as a raw material of a synthetic lubricant, a medical intermediate, a raw material of metal soap and metal processing liquid, is also suitable for modifying alkyd resin, can improve yellowing resistance and impact resistance, can be used for producing various isononanoic acid esters, can be used in the field of cosmetics, and can be used for different applications such as a paint drier, a vinyl stabilizer, a polyvinyl chloride stabilizer, a preservative, a tire bonding aid and the like. Isononanoic acid can be produced by oxidation of the corresponding aldehyde.
At present, metal salt homogeneous catalysts are mostly used for preparing acid by aldehyde oxidation. In patent CN200510054082.9, propionate or acetate or naphthenate is used as a catalyst when propionaldehyde is oxidized to prepare propionic acid. In patent CN02151618.9, the catalyst for preparing acid by aldehyde oxidation is homogeneous manganese salt. Hydroxylamine hydrochloride can also be used as a homogeneous catalyst in H 2 O 2 In the/HCl system, aliphatic aldehydes such as isononanal are efficiently oxidized to their corresponding carboxylic acids in refluxing acetonitrile or methanol. Fatty aldehyde is oxidized to prepare corresponding acid under the combined action of hydrogen peroxide and p-toluenesulfonic acid in the presence of beta-cyclodextrin. The homogeneous system has defects, or the reaction time is long, or the catalyst is dissolved in the reaction system and is difficult to recycle. The sulfonic acid resin is used as a catalyst, the hydrogen peroxide is used as an oxidant, and the aldehyde can be oxidized into corresponding acid, but the activity and the selectivity of the aldehyde are to be improved. The petrochemical oxidation engineering and technology book discloses that the catalyst for the oxidation of aldehydes to carboxylic acids can be acetate or naphthenate, such as: in the device for producing acetic acid by oxidizing acetaldehyde, manganese acetate is used as a catalyst, so that peroxyacetic acid generated during acetaldehyde oxidation is timely decomposed, and the accumulation, decomposition and explosion of the peroxyacetic acid are prevented. But at the same time the metal salt canPromote the generation of free radicals, accelerate the initiation reaction of chains, shorten the induction period of the reaction, obviously shorten the reaction time, but along with the rapid progress of the exothermic reaction, the reaction is difficult to control, and the selectivity is reduced therewith. For example, in the process of preparing propionic acid by oxidizing propionaldehyde, when manganese acetate, cobalt acetate, iron acetate, copper acetate and the like are used as catalysts, the influence of the catalysts on the selectivity of the product is large, and the selectivity is lower than that when the catalysts are not added.
With the continuous and intensive research, it can be found that in the method for synthesizing carboxylic acid by oxidizing aliphatic aldehyde and aromatic aldehyde, due to the existence of side reaction and the restriction of reaction conditions, most products have low purity, low yield and poor economic benefit, and are not beneficial to the industrial production.
Disclosure of Invention
The invention aims to provide a method for preparing isononanoic acid, which has mild reaction conditions and higher yield.
The purpose of the invention can be realized by the following technical scheme: a process for preparing isononanoic acid features that the sulfonated mesoporous Si-C composite material is used as catalyst and hydrogen peroxide is used as oxidant to oxidize isononanoic aldehyde into isononanoic acid.
Further, the preparation method of isononanoic acid specifically comprises the following steps:
(1) Mixing isononanal, acetonitrile, hydrogen peroxide and a sulfonated mesoporous silicon-carbon composite material, heating and reacting;
(2) After the reaction is finished, cooling the reaction mixture to room temperature;
(3) Evaporating acetonitrile in the reaction mixture, adjusting the reaction mixture to be alkaline by using a sodium hydroxide solution, and extracting by using an organic solvent;
(4) Acidifying the water phase obtained by extraction with hydrochloric acid, and extracting with an organic solvent;
(5) The organic phase from the extraction was collected and evaporated to give nonanoic acid.
Furthermore, the reaction temperature in the step (1) is 40-80 ℃, and the reaction time is 1.5-2.5 h;
the concentration of the sodium hydroxide solution in the step (3) is 1.8-2.2 mol/L, and the pH value of the reaction mixture is adjusted to 7.5-8.5;
the concentration of the hydrochloric acid in the step (4) is 5.5-6.5 mol/L, and the pH value of the water phase is adjusted to 1.8-2.2;
the organic solvent used for extraction includes ethyl acetate.
The hydrogen peroxide concentration is 25-35 wt%, and the molar ratio of the sulfonated mesoporous silicon-carbon composite material to the hydrogen peroxide to the isononanal is 0.04-0.16.
The preparation process of the sulfonated mesoporous silicon-carbon composite material comprises the following steps:
(1) Preparing mesoporous silicon by adopting a sol-gel method;
(2) Adding concentrated sulfuric acid into the mesoporous silicon;
(3) Loading sucrose on the mesoporous silicon treated by concentrated sulfuric acid in the step (2) by adopting a chemical impregnation method;
(4) Carrying out carbonization treatment on the sucrose-loaded mesoporous silicon to obtain a mesoporous silicon-carbon composite material;
(5) Carrying out hydrothermal sulfonation treatment on the mesoporous silicon-carbon composite material to obtain the sulfonated mesoporous silicon-carbon composite material.
Further, the sol-gel method preparation process in the step (1) specifically comprises the following steps:
the first step is as follows: adding dodecylamine into a mixed solution of deionized water, hydrochloric acid and ethanol, and uniformly mixing to prepare a solution A;
the second step is that: uniformly mixing isopropanol and tetraethoxysilane to prepare a solution B;
the third step: slowly dripping the solution B into the solution A under strong stirring;
the fourth step: crystallizing, filtering, washing, drying, grinding and roasting to obtain the mesoporous silicon.
Furthermore, the molar ratio of the deionized water, the hydrochloric acid, the ethanol and the dodecylamine in the first step is 120-130;
the volume ratio of the isopropanol to the tetraethoxysilane in the second step is 0.3-0.4;
and the volume ratio of the solution A to the solution B in the third step is 3-4.
The crystallization reaction temperature of the fourth step is 40-50 ℃, the crystallization time is 18-24 h, the drying temperature is 90-110 ℃, the drying time is 8-12 h, the grinding granularity is 200-800 meshes, the roasting temperature is 500-600 ℃, and the roasting time is 9-11 h.
The process of adding the concentrated sulfuric acid into the mesoporous silicon in the step (2) is specifically as follows: ultrasonically oscillating the mesoporous silicon prepared in the step (1) in water, then adding 98% concentrated sulfuric acid, and continuing to ultrasonically oscillate;
the sucrose loading method in the step (3) specifically comprises the following steps: adding sucrose into the mixture of concentrated sulfuric acid and mesoporous silicon obtained in the step (2), stirring to completely dissolve the sucrose, soaking for a period of time at constant temperature, and then drying and grinding the mixture;
the carbonization treatment process in the step (4) is specifically as follows: and (4) carrying out primary carbonization on the ground product obtained in the step (3), and then carrying out high-temperature carbonization under the protection of inert gas to obtain the mesoporous silicon-carbon composite material.
Further, the molar ratio of concentrated sulfuric acid, water and mesoporous silicon in the step (2) is 0.1-0.2; the mol ratio of the sucrose to the mesoporous silicon in the step (3) is 1.2-1.4, the constant-temperature dipping temperature is 35-45 ℃, the dipping time is 8-12 h, the drying temperature is 90-110 ℃, the drying time is 5-6 h, and the grinding granularity is 200-800 meshes; the preliminary carbonization temperature in the step (4) is 150-170 ℃, the preliminary carbonization time is 5-7 h, the high-temperature carbonization temperature is 750-850 ℃, and the high-temperature carbonization time is 5-7 h.
The hydrothermal sulfonation treatment process in the step (5) comprises the following specific steps: adding concentrated sulfuric acid into the mesoporous silicon-carbon composite material obtained in the step (4) under the protection of inert gas, heating and refluxing, cooling to room temperature after the reaction is finished, diluting, filtering, washing the reaction solution to obtain a concentrated sulfuric acid-treated mesoporous silicon-carbon composite material, then transferring the concentrated sulfuric acid-treated mesoporous silicon-carbon composite material into a hydrothermal reaction kettle, carrying out hydrothermal reaction for a period of time, washing the product to be neutral, and drying to obtain the sulfonated mesoporous silicon-carbon composite material. Further, the mass ratio of the mesoporous silicon-carbon composite material to concentrated sulfuric acid is 0.02-0.03, the heating reflux temperature is 50-70 ℃, the time is 15-16 h, the hydrothermal reaction temperature is 190-210 ℃, the hydrothermal reaction time is 2-4 h, and the drying temperature is 90-110 ℃.
Compared with the prior art, the invention has the following advantages:
1. the reaction conditions required by catalytic oxidation of aldehydes are mild, and a high yield can be obtained at 40-80 ℃;
2. the sulfonated mesoporous silicon-carbon composite material catalyst prepared by the invention is easy to separate and recycle, and has stable performance;
3. the sulfonated mesoporous silicon-carbon composite material catalyst prepared by the invention has large specific surface area and pore volume, and is an excellent environment-friendly catalyst;
4. the invention has less by-products, high product purity, high yield and good economic benefit;
5. the preparation method is simple, high in safety and small in environmental pollution, and accords with the green development concept.
Detailed Description
The following examples are given to illustrate the embodiments of the present invention, and the following examples are given to illustrate the detailed embodiments and specific procedures of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
Preparing a sulfonated mesoporous silicon-carbon composite material catalyst:
into a 150ml three-necked flask, 32.4ml of deionized water, 1.0ml (1 mol/L) was placed -1 ) The aqueous solution of the compound (A) and 19.0ml of absolute ethyl alcohol are mixed uniformly, 2.60g of dodecylamine is added, and the mixture is stirred in a water bath at the temperature of 45 ℃ for 30 minutes to prepare a solution A. 3.8ml of isopropanol and 11.1ml of ethyl orthosilicate are added into a dropping funnel and mixed evenly to prepare liquid B. Slowly dripping the solution B into the solution A under strong stirring, and crystallizing in a water bath at 50 ℃ for 20 hours. And pouring out the sample, performing suction filtration, and fully washing the sample by using deionized water to remove chloride ions. And drying the filter cake in an oven at 100 ℃ for 10 hours, taking out, grinding, transferring into a muffle furnace, and roasting at 550 ℃ for 10 hours to obtain a mesoporous silicon sample. Weighing 1g of mesoporous silicon sample, adding 12ml of water into a beaker, carrying out ultrasonic oscillation for 1.5 hours, adding 0.22g of 98% concentrated sulfuric acid, carrying out ultrasonic oscillation for 0.5 hour, then adding 1.65g of cane sugar, and stirring to ensure thatThe sugar was completely dissolved and immersed in a water bath at 40 ℃ for 10 hours at constant temperature. And (4) transferring the mixture into an oven, and drying the mixture for 5 to 6 hours at the temperature of 100 ℃. Grinding the dried sample, transferring into crucible, roasting in muffle furnace at 160 deg.C for 6 hr for preliminary carbonization, and then N 2 Carbonizing at 800 deg.c for 6 hr under protection to obtain the mesoporous Si-C composite material.
Then weighing about 1g of mesoporous silicon-carbon composite material, placing the mesoporous silicon-carbon composite material in a 100ml three-neck flask, adding 20ml of concentrated sulfuric acid, and adding N 2 Under protection, heating and refluxing for 15-16 h in an oil bath, cooling to room temperature after reaction, diluting the reaction solution with 200ml of deionized water, performing suction filtration, washing with 80 ℃ distilled water for 3 times, transferring into a hydrothermal reaction kettle, performing hydrothermal reaction at 200 ℃ for 3h, and washing with distilled water until the pH of the filtrate is 7. Drying the sample at 100 ℃ to prepare the sulfonated mesoporous silicon-carbon composite.
Example 2
In this embodiment, the catalyst sulfonated mesoporous silicon-carbon composite material prepared in example 1 is used in a reaction for preparing isononanoic acid by catalytic oxidation of isononanoic aldehyde, and the specific process is as follows: adding 2g of isononanal, 4g of acetonitrile, 4g of 30wt% hydrogen peroxide and 0.08g of catalyst into a 25ml single-neck round-bottom flask, heating in an oil bath to control the reaction temperature to be 288K, starting timing after the temperature rises to 313K, cooling to room temperature after reacting for 2h, evaporating the solvent in the reaction mixture through rotary evaporation, adjusting the pH to be 8 by using 2mol/L NaOH solution, extracting by using ethyl acetate, acidifying the water phase by using 6mol/L HCl, adjusting the pH to be 2, extracting by using ethyl acetate, collecting the obtained organic phase, and finally performing rotary evaporation to obtain the carboxylic acid. The isononanoic acid yield was 53%.
Example 3
In this embodiment, the catalyst sulfonated mesoporous silicon-carbon composite material prepared in example 1 is used in a reaction for preparing isononanoic acid by catalytic oxidation of isononanoic aldehyde, and the specific process is as follows: adding 2g of isononanal, 4g of acetonitrile, 4g of 30wt% hydrogen peroxide and 0.08g of catalyst into a 25ml single-neck round-bottom flask, heating in an oil bath to control the reaction temperature to be 288K, starting timing after the temperature is raised to 330K, cooling to room temperature after reacting for 2h, evaporating the solvent in the reaction mixture through rotary evaporation, adjusting the pH to be 8 by using 2mol/L NaOH solution, extracting by using ethyl acetate, acidifying the water phase by using 6mol/L HCl, adjusting the pH to be 2, extracting by using ethyl acetate, collecting the obtained organic phase, and finally performing rotary evaporation to obtain the carboxylic acid. The isononanoic acid yield was 73%.
Example 4
In this embodiment, the sulfonated mesoporous silicon-carbon composite material prepared in example 1 is used in the catalytic oxidation of isononanal to prepare isononanoic acid, and the specific process is as follows: adding 2g of isononanal, 4g of acetonitrile, 4g of 30wt% hydrogen peroxide and 0.12g of catalyst into a 25ml single-neck round-bottom flask, heating in an oil bath to control the reaction temperature to be 288K, starting timing after the temperature is raised to 330K, cooling to room temperature after reacting for 2h, evaporating the solvent in the reaction mixture through rotary evaporation, adjusting the pH to be 8 by using 2mol/L NaOH solution, extracting by using ethyl acetate, acidifying the water phase by using 6mol/L HCl, adjusting the pH to be 2, extracting by using ethyl acetate, collecting the obtained organic phase, and finally performing rotary evaporation to obtain the carboxylic acid. The isononanoic acid yield was 79%.
Example 5
In this embodiment, the sulfonated mesoporous silicon-carbon composite material prepared in example 1 is used in the catalytic oxidation of isononanal to prepare isononanoic acid, and the specific process is as follows: adding 2g of isononanal, 4g of acetonitrile, 4g of 30wt% hydrogen peroxide and 0.12g of catalyst into a 25ml single-neck round-bottom flask, heating by an oil bath to control the reaction temperature to be 288K, starting timing after the temperature is raised to 350K, reacting for 2h, cooling to room temperature, evaporating a solvent in a reaction mixture by rotary evaporation, adjusting the pH to be 8 by using 2mol/L NaOH solution, extracting by using ethyl acetate, acidifying an aqueous phase by using 6mol/L HCl, adjusting the pH to be 2, extracting by using ethyl acetate, collecting an organic phase, and finally performing rotary evaporation to obtain carboxylic acid. The isononanoic acid yield was 83%.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (8)
1. A preparation method of isononanoic acid is characterized in that isononanoic aldehyde is oxidized into isononanoic acid by taking sulfonated mesoporous silicon-carbon composite material as a catalyst and hydrogen peroxide as an oxidant, and the preparation method specifically comprises the following steps:
(1) Mixing isononanal, acetonitrile, hydrogen peroxide and a sulfonated mesoporous silicon-carbon composite material, heating and reacting;
(2) After the reaction is finished, cooling the reaction mixture to room temperature;
(3) Evaporating acetonitrile in the reaction mixture, adjusting the reaction mixture to be alkaline by using a sodium hydroxide solution, and extracting by using an organic solvent;
(4) Acidifying the water phase obtained by extraction with hydrochloric acid, and extracting with an organic solvent;
(5) Collecting the organic phase obtained by extraction, and evaporating to obtain isononanoic acid;
the preparation process of the sulfonated mesoporous silicon-carbon composite material comprises the following steps:
(1) Preparing mesoporous silicon by a sol-gel method;
(2) Adding concentrated sulfuric acid into the mesoporous silicon;
(3) Loading sucrose on the mesoporous silicon treated by concentrated sulfuric acid in the step (2) by adopting a chemical impregnation method;
(4) Carrying out carbonization treatment on the sucrose-loaded mesoporous silicon to obtain a mesoporous silicon-carbon composite material;
(5) Carrying out hydrothermal sulfonation treatment on the mesoporous silicon-carbon composite material to obtain the sulfonated mesoporous silicon-carbon composite material.
2. The method for preparing isononanoic acid according to claim 1, wherein in the preparation process of isononanoic acid, the reaction temperature in the step (1) is 40 to 80 ℃, and the reaction time is 1.5 to 2.5 hours;
the concentration of the sodium hydroxide solution in the step (3) is 1.8 to 2.2mol/L, and the pH of the reaction mixture is adjusted to 7.5 to 8.5;
the concentration of the hydrochloric acid in the step (4) is 5.5 to 6.5mol/L, and the pH value of the water phase is adjusted to 1.8 to 2.2;
the organic solvent used for extraction includes ethyl acetate.
3. The method for preparing isononanoic acid according to claim 1, wherein the concentration of hydrogen peroxide is 25 to 35wt%, and the molar ratio of the sulfonated mesoporous silicon-carbon composite material to the hydrogen peroxide to isononanoic aldehyde is 0.04 to 0.16.
4. The method for preparing isononanoic acid according to claim 1, wherein in the preparation process of the sulfonated mesoporous silicon-carbon composite material, the sol-gel method preparation process in the step (1) is specifically as follows:
the first step is as follows: adding dodecylamine into a mixed solution of deionized water, hydrochloric acid and ethanol, and uniformly mixing to prepare a solution A;
the second step is that: uniformly mixing isopropanol and tetraethoxysilane to prepare a solution B;
the third step: slowly dripping the solution B into the solution A under strong stirring;
the fourth step: crystallizing, filtering, washing, drying, grinding and roasting to obtain the mesoporous silicon.
5. The method for preparing isononanoic acid according to claim 4, wherein the molar ratio of deionized water to hydrochloric acid to ethanol to dodecylamine in the first step is from 120 to 130 to 20 to 24;
the volume ratio of the isopropanol to the tetraethoxysilane in the second step is 0.3 to 0.4;
and the volume ratio of the solution A to the solution B in the third step is 3 to 4.
6. The method for preparing isononanoic acid according to claim 1, wherein in the preparation process of the sulfonated mesoporous silicon-carbon composite material, the process of adding the mesoporous silicon into concentrated sulfuric acid in the step (2) is specifically as follows: ultrasonically oscillating the mesoporous silicon prepared in the step (1) in water, adding 98% concentrated sulfuric acid, and continuing to ultrasonically oscillate;
the sucrose loading method in the step (3) specifically comprises the following steps: adding sucrose into the mixture of concentrated sulfuric acid and mesoporous silicon obtained in the step (2), stirring to completely dissolve the sucrose, soaking for a period of time at constant temperature, and then drying and grinding the mixture;
the carbonization treatment process in the step (4) is specifically as follows: and (4) performing primary carbonization on the product ground in the step (3), and then performing high-temperature carbonization under the protection of inert gas to obtain the mesoporous silicon-carbon composite material.
7. The method for preparing isononanoic acid according to claim 6, wherein in the preparation process of the sulfonated mesoporous silicon-carbon composite material, the molar ratio of concentrated sulfuric acid, water and mesoporous silicon in the step (2) is 0.1 to 0.2; the molar ratio of the sucrose to the mesoporous silicon in the step (3) is 1.2 to 1.4, the constant-temperature impregnation temperature is 35 to 45 ℃, the impregnation time is 8 to 12h, the drying temperature is 90 to 110 ℃, the drying time is 5 to 6h, and the grinding particle size is 200 to 800 meshes; and (4) the initial carbonization temperature is 150-170 ℃, the initial carbonization time is 5-7 h, the high-temperature carbonization temperature is 750-850 ℃, and the high-temperature carbonization time is 5-7 h.
8. The method for preparing isononanoic acid according to claim 1, wherein in the preparation process of the sulfonated mesoporous silicon-carbon composite material, the hydrothermal sulfonation treatment process in the step (5) is specifically as follows: adding concentrated sulfuric acid into the mesoporous silicon-carbon composite material obtained in the step (4) under the protection of inert gas, heating and refluxing, cooling to room temperature after the reaction is finished, diluting, filtering, washing the reaction solution to obtain a concentrated sulfuric acid-treated mesoporous silicon-carbon composite material, then transferring the concentrated sulfuric acid-treated mesoporous silicon-carbon composite material into a hydrothermal reaction kettle, carrying out hydrothermal reaction for a period of time, washing the product to be neutral, and drying to obtain the sulfonated mesoporous silicon-carbon composite material.
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| CN103319344A (en) * | 2013-06-06 | 2013-09-25 | 陕西师范大学 | 1,1-diacetate synthesis catalyzed by sulfonated cage-type mesoporous carbon |
| CN104520257A (en) * | 2012-07-13 | 2015-04-15 | Oxea有限责任公司 | Method for producing isononanoic acid esters, starting from 2-ethyl hexanol |
| JP2019203108A (en) * | 2018-05-25 | 2019-11-28 | 旭化成株式会社 | Fine cellulose-containing resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104520257A (en) * | 2012-07-13 | 2015-04-15 | Oxea有限责任公司 | Method for producing isononanoic acid esters, starting from 2-ethyl hexanol |
| CN103319344A (en) * | 2013-06-06 | 2013-09-25 | 陕西师范大学 | 1,1-diacetate synthesis catalyzed by sulfonated cage-type mesoporous carbon |
| JP2019203108A (en) * | 2018-05-25 | 2019-11-28 | 旭化成株式会社 | Fine cellulose-containing resin composition |
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